WO2019054301A1 - Procédé de purification d'un polymère hyper-ramifié contenant un groupe sulfo et son procédé de production - Google Patents

Procédé de purification d'un polymère hyper-ramifié contenant un groupe sulfo et son procédé de production Download PDF

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Publication number
WO2019054301A1
WO2019054301A1 PCT/JP2018/033252 JP2018033252W WO2019054301A1 WO 2019054301 A1 WO2019054301 A1 WO 2019054301A1 JP 2018033252 W JP2018033252 W JP 2018033252W WO 2019054301 A1 WO2019054301 A1 WO 2019054301A1
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sulfo group
sulfuric acid
branched polymer
purifying
group
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PCT/JP2018/033252
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English (en)
Japanese (ja)
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悠太朗 津田
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日産化学株式会社
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Priority to JP2019542033A priority Critical patent/JP7099466B2/ja
Priority to CN201880059465.0A priority patent/CN111094372B/zh
Publication of WO2019054301A1 publication Critical patent/WO2019054301A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates

Definitions

  • the present invention relates to a method for purifying a sulfo group-containing highly branched polymer and a method for producing the same.
  • the highly branched polymer having a sulfo group can not only be used as a dispersant for carbon nanotubes (CNT), but can also be suitably used as a film-forming composition by dissolving it in various solvents.
  • hyperbranched polymer examples include hyperbranched polymers containing a triarylamine structure as a branch point, etc.
  • a sulfo group When introducing a sulfo group into such a polymer, generally, a triaryl group having a sulfo group introduced.
  • polymer raw materials such as an amine compound, an aldehyde compound and a ketone compound
  • a method of treating with a reagent capable of introducing a sulfo group after synthesizing a hyper-branched polymer having no sulfo group is often used in consideration of the simplicity of production.
  • a method of introducing a sulfo group it can be selected from conventionally known methods, and it is not particularly limited, but using a method of sulfonation using an excessive amount of sulfuric acid, etc. it can.
  • Purification of the sulfo group-containing highly branched polymer is carried out by a reprecipitation operation in which a sulfuric acid solution of the polymer is dropped into a poor solvent, but when water is selected as a poor solvent for the reprecipitation solvent, the reprecipitation operation is performed.
  • the particle size of the resulting polymer particles is small, and the filterability of the subsequent precipitates is extremely poor. Due to this poor filterability, problems such as a decrease in production efficiency due to prolonged filtration, an interruption of work due to clogging of fine particles, and an increase in the amount of residual sulfuric acid to the polymer occur.
  • An object of the present invention is to provide a method for purifying a branched polymer and a method for producing a sulfo group-containing highly branched polymer capable of more efficiently producing a sulfo group-containing highly branched polymer.
  • the present inventor put a sulfuric acid solution of a sulfo group-containing highly branched polymer into water to perform reprecipitation treatment, and then further add an organic solvent to the solution containing the precipitate. By adding and stirring, precipitates are aggregated and grown, and high operability such as good filterability is obtained, and it is found that excellent purification effect can be obtained even with a low amount of residual sulfuric acid, the present invention Completed.
  • a sulfuric acid solution of a sulfo group-containing hyperbranched polymer is introduced into water to reprecipitate the sulfo group-containing hyperbranched polymer, and a liquid containing the precipitate obtained in the reprecipitation process and an organic solvent And a flocculating step of agglomerating the precipitate by aggregating the precipitate by mixing and stirring the sulfo group-containing highly branched polymer, 2.
  • the mass ratio of water to the mass of sulfuric acid is 0.95 to 1.25
  • the mass ratio of the organic solvent to the mass of sulfuric acid organic solvent / sulfuric acid
  • a method of producing a sulfo group-containing hyper-branched polymer comprising: a flocculating step of mixing a solution containing water and an organic solvent miscible with water and stirring to flocculate the precipitate; 12. The method for producing a sulfo group-containing highly branched polymer of 11, wherein the organic solvent is tetrahydro
  • the polymer particles are appropriately aggregated by mixing and stirring the solution containing the precipitate after reprecipitation treatment and the organic solvent, so that the operability such as the filterability of the precipitate is excellent. Become.
  • the filtration time is shortened by the drastic improvement of the filterability, it can contribute to the improvement of the productivity, and furthermore, since it is possible to easily carry out the washing of the filtrate, the residual sulfuric acid in the polymer The amount can be reduced sufficiently.
  • the method for purifying a sulfo group-containing hyperbranched polymer of the present invention comprises the steps of: re-precipitation treatment step of re-precipitating the sulfo group-containing hyper branched polymer by charging a sulfuric acid solution of sulfo group-containing hyperbranched polymer after polymerization reaction into water
  • the liquid containing the precipitate obtained at the said re-precipitation process process and an organic solvent are mixed, and it stirs, and the aggregation process of aggregating the said precipitate is included.
  • a re-precipitation process process is a process of throwing the sulfuric acid solution of a sulfo-group containing hyperbranched polymer into water, and reprecipitating the said sulfo-group containing hyper-branched polymer.
  • the sulfuric acid solution of the sulfo group-containing hyperbranched polymer may be a solution prepared by dissolving the sulfo group-containing hyperbranched polymer in sulfuric acid, or a reaction solution after sulfonation of the hyperbranched polymer in sulfuric acid.
  • the reaction solution after sulfonation is preferred.
  • the mass of sulfuric acid means the mass of sulfuric acid used in dissolving the sulfo group-containing hyperbranched polymer, which is high
  • a reaction solution after sulfonation of a branched polymer in sulfuric acid it means the mass of sulfuric acid used in sulfonation of the hyperbranched polymer. For example, if 40 g of 95% strength by weight sulfuric acid is used in the sulfonation of the hyperbranched polymer, the weight of sulfuric acid used is 38 g.
  • sulfuric acid that can be used for the sulfuric acid solution of the sulfo group-containing highly branched polymer, concentrated sulfuric acid, fuming sulfuric acid and the like can be mentioned, but concentrated sulfuric acid can be particularly preferably used from the viewpoint of cost and handling.
  • concentration of the sulfuric acid is also not particularly limited, but is preferably 90% by mass or more, more preferably 95% by mass or more, in consideration of efficiently precipitating the polymer. (Hereafter, it may be simply expressed as%.)
  • the amount of sulfuric acid used in the sulfuric acid solution of the sulfo group-containing highly branched polymer is not particularly limited, but when using a solution prepared by dissolving the sulfo group-containing hyper branched polymer in sulfuric acid, the sulfo group-containing high When using the reaction solution after sulfonation of the hyperbranched polymer in sulfuric acid with respect to the branched polymer, 2 to 50 times by mass is preferable, and 10 to 30 mass times with respect to the raw material polymer before sulfonation. Double is more preferable.
  • the amount of water used in the reprecipitation treatment step is not particularly limited, but from the viewpoint of rapidly reprecipitating the sulfo group-containing highly branched polymer, the mass ratio of water to the mass of sulfuric acid (water / sulfuric acid) is 0.
  • the ratio is preferably 5 to 2, and more preferably 0.95 to 1.25, and most preferably 1 to 1.21, from the viewpoint of appropriately controlling the aggregation of the hyperbranched polymer to further improve the filterability.
  • the temperature (internal temperature) of the liquid during the reprecipitation treatment is not particularly limited, but is preferably controlled in the range of 25 to 100 ° C., more preferably 30 to 60 ° C., from the viewpoint of promoting aggregation. .
  • the aggregation step is a step of mixing the liquid containing the precipitate obtained in the reprecipitation treatment step and an organic solvent, and stirring to appropriately aggregate the precipitate.
  • the organic solvent is not particularly limited as long as it is a solvent capable of aggregating the target sulfo group-containing hyperbranched polymer, and examples thereof include protic organic solvents and aprotic organic solvents.
  • protic organic solvent examples include alcohol solvents such as methanol, ethanol and 2-propanol.
  • aprotic organic solvents include nitrile solvents such as acetonitrile, cyclic ether solvents such as tetrahydrofuran and dioxane, and amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, and dimethylacetamide.
  • sulfoxide solvents such as dimethyl sulfoxide.
  • the organic solvent is preferably miscible with water in any proportion among those exemplified above, and from the viewpoint of being able to appropriately control the aggregation of the hyperbranched polymer, tetrahydrofuran, acetonitrile, dioxane or a mixed solvent thereof is preferred.
  • tetrahydrofuran, dioxane or a mixed solvent thereof is more preferable, and tetrahydrofuran is more preferable.
  • the amount of the organic solvent used is not particularly limited, but the mass ratio of the organic solvent to the mass of sulfuric acid (organic solvent / sulfuric acid) is preferably 0.5 to 1.5, and the aggregation of the highly branched polymer is appropriately controlled. In order to further improve the filterability, 0.5 to 1.1 is more preferable, 0.9 to 1.1 is more preferable, and 0.95 to 1.05 is most preferable.
  • the temperature (internal temperature) of the solution is preferably 25 to 100 ° C., more preferably 30 to 60 ° C., from the viewpoint of appropriately controlling aggregation of the hyperbranched polymer to further improve the filterability.
  • the stirring time is preferably 2 hours or more, more preferably 4 hours or more, from the viewpoint of aggregating fine particles having a particle size of less than 1 ⁇ m.
  • the upper limit is not particularly limited, but is preferably 50 hours or less, and more preferably 25 hours or less.
  • the total amount of sulfuric acid, water and organic solvent used is preferably 5 to 200 times by mass, more preferably 20 to 100 times by mass, still more preferably 40 to 80 times by mass that of the raw material polymer before sulfonation. If the total amount used is out of the above range, aggregation may not proceed.
  • the filtration equipment is not particularly limited, and a known suction filtration equipment or the like may be used.
  • the drying temperature and time can not be generally defined because they differ depending on the type of the organic solvent, the heat resistance of the polymer, etc., but the temperature is about 50 to 200 ° C., preferably about 80 to 150 ° C., 1 to 200 hours It is an extent.
  • the pressure may be reduced to about -10 to -100 kPa.
  • the residual sulfuric acid can be reduced to about 1,000 ppm or less, and in some cases to about 200 ppm or less, for the sulfo group-containing highly branched polymer.
  • the sulfo group-containing hyper-branched polymer to which the purification method of the present invention can be applied is not particularly limited as long as it contains a sulfo group in its structure, for example, a hyper-branched polymer having a triarylamine structure (e.g. No.
  • the purification method of the present invention is a hyperbranched polymer having a triarylamine structure, more specifically, a novolak type hyperbranched polymer obtained by polymerizing a triarylamine compound and an aldehyde compound It can employ
  • the novolac hyperbranched polymer can be obtained by polymerizing a triarylamine compound and an aldehyde compound according to the method described in the above-mentioned WO 2011/065395, but in particular, gelation of the product and viscosity increase From the viewpoint of avoiding problems in the production of wall deposits etc., a production method including the following polymerization step and sulfonation step can be adopted as a more preferable method.
  • the polymerization step is a step of polymerizing a triarylamine compound and an aldehyde compound to obtain a novolak-type highly branched polymer.
  • the triarylamine compound is preferably a triarylamine compound represented by the following formula (A).
  • Ar 1 to Ar 3 each independently represent a divalent organic group represented by any one of Formulas (A-1) to (A-5).
  • the group represented by -1) is preferred.
  • R 1 to R 34 each independently represent a hydrogen atom, a halogen atom, an alkyl group of 1 to 5 carbon atoms or an alkoxy group of 1 to 5 carbon atoms .
  • halogen atom a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
  • the alkyl group having 1 to 5 carbon atoms is preferably linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and an isobutyl group. And tert-butyl group, n-pentyl group and the like.
  • the alkoxy group having 1 to 5 carbon atoms is preferably linear or branched, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group and an isobutoxy group. Groups, tert-butoxy group, n-pentyloxy group and the like.
  • Preferred triarylamine compounds include triphenylamine and derivatives thereof.
  • the aldehyde compound is not particularly limited, but is preferably one represented by the following formula (B).
  • each R independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a monovalent organic group represented by any one of the following formulas (B-1) to (B-4). It is a group.
  • R 35 to R 58 each independently represent a hydrogen atom, a halogen atom, an alkyl group of 1 to 5 carbon atoms, a haloalkyl group of 1 to 5 carbon atoms, or phenyl group, -OR 59, -COR 60, a -NR 61 R 62 or -COOR 63, R 59 ⁇ R 62 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, 1 to 5 carbon atoms And R 63 is an alkyl group of 1 to 5 carbon atoms, a haloalkyl group of 1 to 5 carbon atoms or a phenyl group.
  • the haloalkyl group having 1 to 5 carbon atoms is preferably linear or branched, and examples thereof include difluoromethyl group, trifluoromethyl group, bromodifluoromethyl group, 2-chloroethyl group, 2-bromoethyl group, 1, 1-difluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 2-chloro-1,1,2-trifluoroethyl group, pentafluoroethyl group, 3-bromopropyl, 2,2,3,3-tetrafluoropropyl, 1,1,2,3,3,3-hexafluoropropyl, 1,1,1,3,3,3-hexafluoro Examples include propan-2-yl group, 3-bromo-2-methylpropyl group, 4-bromobutyl group, perfluoropentyl group and the like.
  • an aromatic aldehyde compound is preferable.
  • R is a group represented by any of the formulas (B-1) to (B-4) is preferable, and 2- or 3 is preferable.
  • -Thienyl group or a group represented by the formula (B-1) is preferable, and 2- or 3-thienyl group or R 37 in the group represented by the formula (B-1) is a phenyl group It is more preferable that there is a certain one or a methoxy group, and still more preferable that the R 37 in the 2- or 3-thienyl group or the group represented by the formula (B-1) is a phenyl group.
  • Preferred aldehyde compounds include benzaldehyde, 4-methyl benzaldehyde, 3-trifluoromethyl benzaldehyde, 4-trifluoromethyl benzaldehyde, 3-phenyl benzaldehyde, 4-phenyl benzaldehyde, salicylaldehyde, anisaldehyde, 4-acetoxy benzaldehyde, and 4-acetoxy benzaldehyde Acetylbenzaldehyde, 2-formylbenzoic acid, 3-formylbenzoic acid, 4-formylbenzoic acid, methyl 2-formylbenzoate, methyl 3-formylbenzoate, methyl 4-formylbenzoate, 4-aminobenzaldehyde, 4-dimethyl Aminobenzaldehyde, 4-diphenylaminobenzaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, 2-thiophenecarbaldeh
  • Hyperbranched polymers By polymerizing the triarylamine compound represented by the formula (A) and the aldehyde compound represented by the formula (B) in the presence of an acid catalyst, it contains a repeating unit represented by the following formula (C) Hyperbranched polymers can be synthesized.
  • hyperbranched polymer examples include those having a repeating unit represented by the following formula, but are not limited thereto.
  • the amount of the aldehyde compound represented by the formula (B) is preferably 0.1 to 1.0 equivalent of the aldehyde compound per 1 equivalent of the triarylamine compound represented by the formula (A), and 0.7 -0.95 equivalents are more preferred.
  • the average molecular weight of the hyperbranched polymer is not particularly limited, but the weight average molecular weight (Mw) is preferably 1,000 to 2,000,000, and more preferably 2,000 to 200,000.
  • Mw is a polystyrene conversion value measured by gel permeation chromatography (GPC).
  • the acid catalyst examples include inorganic acids such as sulfuric acid, phosphoric acid and perchloric acid, sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid and camphorsulfonic acid, and organic acids such as carboxylic acids such as formic acid and oxalic acid Although sulfuric acid and sulfonic acid are preferred.
  • the amount of the acid catalyst to be used is appropriately set depending on the type thereof, but generally 0.01 to 0.5 equivalent is preferable, and 0.02 to 0.2 equivalent is more preferable, with respect to 1 equivalent of the triarylamine compound.
  • the compound is synthesized by condensation polymerization of the triarylamine compound and an aldehyde compound, but water is generated as a by-product because dehydration occurs at this time.
  • the method of removing the by-product water is not particularly limited, but a method of removing by azeotropy is preferable from the viewpoint of mass production.
  • a method of removing water by azeotropy for example, a method of removing by-produced water using a Dean-Stark apparatus can be mentioned.
  • the organic solvent it is preferable to be azeotropic with water, smaller in specific gravity than water, and immiscible with water.
  • immiscible with water refers to an organic solvent in which the amount of water to be dissolved is less than 5.0% by mass.
  • organic solvents include aromatic hydrocarbons such as toluene, o-xylene, m-xylene and p-xylene, aliphatic hydrocarbons such as heptane, hexane and cyclohexane, diethyl ether, cyclopentyl methyl ether and the like Ethers, ketones such as 2-methyltetrahydrofuran, 4-methyltetrahydropyran, methyl isobutyl ketone and the like can be mentioned. Among these, toluene, o-xylene, m-xylene, p-xylene or mixtures thereof are preferable.
  • the amount of the organic solvent used is preferably 1 to 50, and more preferably 2 to 10 in mass ratio with respect to the total of the triarylamine compound and the aldehyde compound.
  • the temperature at the time of the polymerization reaction may be appropriately set depending on the raw material and the solvent to be used, but is usually 40 to 200 ° C. Also, as described above, when water is removed azeotropically using a Dean-Stark apparatus, the reaction is carried out at the reflux temperature, but at this time the external temperature is 1 ° C. higher than the internal temperature (reflux temperature) to sufficiently reflux. It is preferable to set higher than the above, and it is more preferable to set 10 ° C. or more higher than the internal temperature.
  • the upper limit of the external temperature is not particularly limited, but is usually about the internal temperature + 20 ° C.
  • the reaction time is appropriately selected depending on the reaction temperature, but is usually about 1 to 30 hours.
  • the resulting hyperbranched polymer is subjected to the next sulfonation step as it is or after being purified to a solid state.
  • the sulfonation step is a step of introducing a sulfo group into the hyperbranched polymer obtained in the polymerization step, but the method of introducing a sulfo group is not particularly limited, and, for example, an excessive amount of A method such as sulfonation using sulfuric acid can be used (for example, WO 2012/161307 etc.).
  • sulfuric acid concentrated sulfuric acid, fuming sulfuric acid and the like can be used, and concentrated sulfuric acid can be suitably adopted from the viewpoint of cost and handling.
  • 90 mass% or more is preferable, and, as for the density
  • the amount of sulfuric acid used for sulfonation is not particularly limited, but is preferably 100 parts by mass or less with respect to 1 part by mass of the hyperbranched polymer, and 50 mass in consideration of operations such as heat generation control at the time of charging into water at post treatment. It is more preferably at most 30 parts by mass. Although a minimum in particular is not restrict
  • the reaction temperature in the sulfonation may be appropriately set according to the raw material and solvent to be used, but it is usually 20 to 100 ° C., preferably 30 to 60 ° C.
  • the reaction time is appropriately selected depending on the reaction temperature, but is usually about 1 to 24 hours, and is not particularly limited as long as it is 1 hour or more.
  • sulfo group-containing highly branched polymer those having a sulfo group introduced on the aromatic ring of the repeating unit of the polymer are preferable, and those having a repeating unit represented by the following formula are mentioned as a more preferable specific example However, it is not limited to this.
  • the sulfo group-containing hyperbranched polymer is obtained as a sulfuric acid solution, and the reaction solution is used as it is or as a solid after removal of a solvent and the like, and is subjected to the above-mentioned reprecipitation step.
  • IGF-100 Device ion chromatograph: Nippon Dionex Co., Ltd.
  • ICS-1500 10 mL of 5 mM NaOH was added to 1 mg of the sample, shaken well, and liquid-liquid extraction was performed. The aqueous phase was measured by ion chromatography, and the amount of sulfuric acid extracted to the aqueous phase was measured and quantified.
  • Example 1 In a 50 mL flask, 40 g of 95% concentrated sulfuric acid (manufactured by Junsei Chemical Co., Ltd.) was charged and the internal temperature was adjusted to 35-45 ° C., and then 2 g of the raw material polymer PTPA obtained in Synthesis Example 1 was charged. Then, after stirring at an internal temperature of 35 to 45 ° C. for 3 hours, the solution was cooled to around room temperature to obtain a sulfuric acid solution of sulfonated PTPA (hereinafter, PTPA-S). After 44 g of water was charged into a separately prepared 200 mL flask, the obtained PTPA-S sulfuric acid solution was added dropwise while maintaining the internal temperature at 30 ° C.
  • PTPA-S sulfuric acid solution of sulfonated PTPA
  • Comparative Example 1 40 g of 95% concentrated sulfuric acid (manufactured by Junsei Chemical Co., Ltd.) was charged into a 50 mL flask and the internal temperature was adjusted to 35-45 ° C., and 2 g of the raw material polymer PTPA obtained in Synthesis Example 1 was charged. Then, after stirring for 3 hours at an internal temperature of 35 to 45 ° C., the solution was cooled to around room temperature to obtain a sulfuric acid solution of PTPA-S. After 86 g of water was charged into a separately prepared 200 mL flask, the obtained PTPA-S sulfuric acid solution was added dropwise while maintaining the internal temperature at 30 ° C. or lower to perform reprecipitation operation.
  • 95% concentrated sulfuric acid manufactured by Junsei Chemical Co., Ltd.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Phenolic Resins Or Amino Resins (AREA)
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Abstract

La présente invention concerne un procédé de purification d'un polymère hyper-ramifié contenant un groupe sulfo caractérisé en ce qu'il comprend une étape de re-précipitation qui introduit une solution d'acide sulfurique d'un polymère hyper-ramifié contenant un groupe sulfo dans de l'eau pour re-précipiter le polymère hyper-ramifié contenant un groupe sulfo, et une étape d'agrégation qui mélange et agite une solution contenant le précipité obtenu dans l'étape de re-précipitation et un solvant organique pour agréger le précipité.
PCT/JP2018/033252 2017-09-15 2018-09-07 Procédé de purification d'un polymère hyper-ramifié contenant un groupe sulfo et son procédé de production WO2019054301A1 (fr)

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JP2019542033A JP7099466B2 (ja) 2017-09-15 2018-09-07 スルホ基含有高分岐ポリマーの精製方法及びその製造方法
CN201880059465.0A CN111094372B (zh) 2017-09-15 2018-09-07 含有磺基的高支化聚合物的精制方法及其制造方法

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JP2017-177930 2017-09-15

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012161307A1 (fr) * 2011-05-25 2012-11-29 日産化学工業株式会社 Polymère hautement ramifié et dispersant pour des nanotubes de carbone
WO2012161306A1 (fr) * 2011-05-25 2012-11-29 日産化学工業株式会社 Composition conductrice et complexe conducteur
JP2012245441A (ja) * 2011-05-25 2012-12-13 Nissan Chem Ind Ltd カーボンナノチューブ分散剤
JP2013006756A (ja) * 2011-05-25 2013-01-10 Nissan Chem Ind Ltd カーボンナノチューブ分散材料の導電性向上方法
WO2014042080A1 (fr) * 2012-09-14 2014-03-20 日産化学工業株式会社 Collecteur de courant composite destiné à une électrode de dispositif de stockage d'énergie, et électrode
WO2016035823A1 (fr) * 2014-09-02 2016-03-10 国立大学法人九州大学 Matériau de gainage à faible résistance et guide d'ondes optiques polymère électro-optique
WO2016117524A1 (fr) * 2015-01-23 2016-07-28 日産化学工業株式会社 Procédé de purification de polymère contenant un cycle triazine
WO2016117531A1 (fr) * 2015-01-23 2016-07-28 日産化学工業株式会社 Procédé de purification d'un polymère contenant un cycle de triazine

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012161307A1 (fr) * 2011-05-25 2012-11-29 日産化学工業株式会社 Polymère hautement ramifié et dispersant pour des nanotubes de carbone
WO2012161306A1 (fr) * 2011-05-25 2012-11-29 日産化学工業株式会社 Composition conductrice et complexe conducteur
JP2012245441A (ja) * 2011-05-25 2012-12-13 Nissan Chem Ind Ltd カーボンナノチューブ分散剤
JP2013006756A (ja) * 2011-05-25 2013-01-10 Nissan Chem Ind Ltd カーボンナノチューブ分散材料の導電性向上方法
WO2014042080A1 (fr) * 2012-09-14 2014-03-20 日産化学工業株式会社 Collecteur de courant composite destiné à une électrode de dispositif de stockage d'énergie, et électrode
WO2016035823A1 (fr) * 2014-09-02 2016-03-10 国立大学法人九州大学 Matériau de gainage à faible résistance et guide d'ondes optiques polymère électro-optique
WO2016117524A1 (fr) * 2015-01-23 2016-07-28 日産化学工業株式会社 Procédé de purification de polymère contenant un cycle triazine
WO2016117531A1 (fr) * 2015-01-23 2016-07-28 日産化学工業株式会社 Procédé de purification d'un polymère contenant un cycle de triazine

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CN111094372B (zh) 2022-10-21
TWI783039B (zh) 2022-11-11
JPWO2019054301A1 (ja) 2020-10-15
TW202017961A (zh) 2020-05-16
JP7099466B2 (ja) 2022-07-12
CN111094372A (zh) 2020-05-01

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